The present invention relates to oxidized polyolefin waxes having a molecular weight Mw in the range from 1000 to 40,000 g/mol, obtainable by oxidizing polyolefins prepared by catalysis using a single-site catalyst based on a complex of a transition metal from groups 5 to 8 of the Periodic Table of the Elements containing not more than one cyclopentadienyl system per metal atom.
The present invention also relates to a process for preparing oxidized polyolefin waxes by oxidizing polyolefins having a molecular weight Mw in the range from 1000 to 40,000 g/mol with oxygen agents at a temperature in the range from 140 to 350xc2x0 C., and to the use of oxidized waxes as or in coating, floorcare or leathercare compositions, and also to the use of oxidized polyolefin waxes as or in coating compositions for citrus fruits.
Oxidized polyolefin waxes are known as such. They are generally obtained by oxidizing usually low molecular mass Ziegler polyethylene, Phillips polyethylene (PE-HD) or else high pressure polyethylene (PE-LD) using air or pure oxygen; see, for example, Kunststoff-Handbuch, Vol. 4, p. 161 ff., Carl-Hanser-Verlag, 1969.
Such oxidized waxes are used as coating compositions for various fields: in the surface treatment of floors or citrus fruits, for example.
The oxidation of polyolefin waxes is accompanied by the formation, inter alia, of carboxyl groups in or on the polymer chains of the polyolefin starting material, the number of these groups being determinable by way of what is known as the acid number. A high acid number in the waxes is generally of advantage, since the waxes can be dispersed and employed more effectively.
During the oxidation of known Phillips polyethylene, Ziegler polyethylene or, in particular, high-pressure polyethylene waxes, a sharp reduction is observed in the melting points of the oxidized waxes relative to the polymer starting materials, and goes hand in hand with an unwanted reduction in the hardness of the oxidized waxes. For use as or in coating compositions, in floorcare compositions or in the preservation of citrus fruits, for example, however, high hardness and thus a high melting point of the oxidized waxes are advantageous.
DE-A 196 17 230 discloses oxidized polyethylene waxes obtained by oxidizing waxes prepared by metallocene catalysis.
Moreover, EP-A 0 890 583 discloses a process for oxidizing polyethylene waxes where organic or inorganic acids are added to the polyethylene melt.
However, relative to the starting materials, the melt viscosities of the waxes obtainable in accordance with DE-A 196 17 230 and EP-A 0 890 583 are greatly reduced. This is due to degradation of the polymer chains. Severe degradation of the polymer chains, however, is disadvantageous, since it results in a deterioration in the performance properties. In particular, there is still room for improvement in the hardness in applications of the prior art oxidized waxes in or as floorcare or coating compositions for citrus fruits, for example.
Additionally, the reaction times for the oxidation run to several hours and are therefore disadvantageously long, reducing the capacity of the plant.
It is an object of the present invention to remedy the above disadvantages and, in particular, to provide oxidized polyolefin waxes combining a relatively high molecular weight with a high acid number, high saponification number, comparatively high hardness, and high melting point.
A further object of the present invention is to provide an oxidation process for polyolefins allowing access to oxidized polyolefin waxes having the desired properties specified in the preceding paragraph.
We have found that these objects are achieved by oxidized waxes which were prepared by oxidizing polyolefin waxes obtained by catalysis using selected complexes of transition metals from groups 5 to 8 of the Periodic Table of the Elements. The oxidized waxes of the invention have a molecular weight Mw in the range from 1000 to 40,000 g/mol. We have also found a process for preparing the oxidized polyolefin waxes of the invention by oxidizing polyolefins having a molecular weight Mw in the range from 1000 to 40,000 g/mol with oxygen agents at a temperature in the range from 140 to 350xc2x0 C.
We have additionally found the use of oxidized waxes as or in coating compositions, the use of oxidized waxes as or in floorcare compositions, and the use of oxidized waxes as or in coating compositions for citrus fruits.
The polyolefins on which the oxidized waxes are based have a weight average molecular weight Mw, determined by the method of gel permeation chromatography (GPC) in 1,2,4-trichlorobenzene at 135xc2x0 C. using polyethylene or polypropylene standards, in the range from 1000 to 40,000 g/mol, preferably in the range from 2000 to 20,000 g/mol. The polydispersity Mw/Mn of the polyolefins on which the oxidized waxes are based, measured by the method of GPC as described, is generally in the range from 1.5 to 3.0, preferably in the range from 1.8 to 2.5.
The polyolefins on which the oxidized waxes are based may be obtained by polymerizing the corresponding monomers in the presence of complexes of the formulae I a to c.
Waxes preparable using such single-site catalysts of a transition metal from groups 5 to 8 of the Periodic Table, containing not more than one cyclopentadienyl system per transition metal atom, are known per se. In one embodiment the single-site catalysts comprise as catalytically active component a tri-pnicogen-cyclohexane complex of a transition metal from groups 5 to 8 of the Periodic Table. Such tri-pnicogen-cyclohexane complexes are, for example, a 1,3,5-triazacyclohexane complex, a 1,3-dia-za-5-phosphacyclohexane complex or a 1,3,5-triphosphacyclohexane complex of a transition metal from groups 5 to 8 of the Periodic Table. The chromium complexes required for this preparation comprise compounds of the formula I a to c.
In formula I a 
M is an element from the group consisting of V, Nb, Ta, Cr, Mo, W, Mn, and Fe in the +3 oxidation state; preferably V, Cr or Mo, and with particular preference Cr;
X1 and X2 are selected from
halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being particularly preferred;
trifluoroacetate,
BF4 less than , PF6xe2x88x92or SbF6xe2x88x92,
C1-C18 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C1-C6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, with particular preference C1-C4 alkyl such as methyl, ethyl, n-propyl and n-butyl;
C3-C12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred,
C7 to C20 aralkyl, preferably C7 to C12 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, with particular preference benzyl,
C6-C14 aryl such asphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, with particular preference phenyl;
C1-C12 alkoxy, preferably C1-C6 alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy and isohexoxy, with particular preference methoxy, ethoxy, n-propoxy and n-butoxy; or
NR8R9, where R8 and R9 independently of one another are selected from hydrogen, C1-C12 alkyl, C2-C12 alkenyl and C6-C14 aryl, which may form a saturated or unsaturated 5- to 10-membered ring; preference is given to the dimethylamino, the diethylamino, the diisopropylamino, the methylphenylamino, and the diphenylamino group. Examples of amino groups with saturated rings are the N-piperidyl group and the N-pyrrolidinyl group; examples of amino groups with unsaturated rings are the N-pyrryl group, the N-indolyl group, and the N-carbazolyl group.
Preferably, X1 and X2 are the same; with very particular preference, X1 and X2 are chlorine.
R1 to R6 are, independently of one another,
hydrogen;
halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred;
C1-C18 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C1-C6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, with particular preference C1-C4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
C1-C12 alkyl substituted one or more times by donor atoms, e.g., noncyclic or cyclic ethers, alcohols, ketals, thioethers or amines; for example, methoxymethyl, ethoxymethyl, ethoxyethyl, xcex2-hydroxyethyl, xcfx89-ethoxypropyl, (2-ethylhexyloxy)propylidene, methoxyethoxypropylidene or xcfx89-dimethylaminopropyl;
mono- or polyhalogenated C1-C12 alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, with particular preference fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
C2-C12 alkenyl, preferably C2 to xcfx89-C8 alkenyl such as vinyl, allyl, but-3-en-1-yl, xcfx89-pentenyl, xcfx89-hexenyl, xcfx89-heptenyl, and xcfx89-octenyl;
C3-C12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
C7 to C20 aralkyl, preferably C7 to C12 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, with particular preference benzyl;
C6-C14 aryl such asphenyl, l-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, with particular preference phenyl;
silyl SiR10R11R12, R10 to R12 independently of one another being selected from hydrogen, C1-C12 alkyl, C7-C15 aralkyl and C6-C14 aryl; preference is given to the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylylsilyl group; particular preference is given to the trimethylsilyl group and the tert-butyldimethylsilyl group;
siloxy OSiR10R11R12, R10 to R12 independently of one another being selected from hydrogen, C1-C12 alkyl, C7-C15 aralkyl and C6-C14 aryl; preference is given to the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxy and the tri-para-xylylsilyloxy group; particular preference is given to the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group;
C1-C12 alkoxy, preferably C1-C6 alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy and isohexoxy, with particular preference methoxy, ethoxy, n-propoxy and n-butoxy;
C6-C14 aryl, substituted in turn by one or more C1-C12 alkyl, C1-C12 alkenyl, C3-C12 cycloalkyl, C6-C14 aryl, silyl SiR10R11R12, siloxy OSiR10R11R12 or C1-C12 alkoxy groups, these groups being as specified above;
A1 is, R13 being selected from halogen, C1-C12 alkyl, Oxe2x80x94R13, Sxe2x80x94R13, N(R13)2 or P(R13)2C2-C12 alkenyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C14 aryl groups or C1-C12 alkoxy groups, these groups being as defined for R1 to R6.
In one particular embodiment of the present invention, two adjacent radicals may together and including the parent aromatic form a 5- to 10-membered ring. So in formula I a, for example, R3 and R4 may together be the following: xe2x80x94(CH2)3xe2x80x94 (trimethylene), xe2x80x94(CH2)4xe2x80x94 (tetramethylene), xe2x80x94(CH2)5xe2x80x94 (pentamethylene), xe2x80x94(CH2)6xe2x80x94(hexamethylene), xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94CH2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Oxe2x80x94CH2xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CH(CH3)xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CHxe2x80x94(C6H5)xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94C(CH3)2xe2x80x94Oxe2x80x94, xe2x80x94NCH3xe2x80x94CH2xe2x80x94CH2xe2x80x94NCH3xe2x80x94, xe2x80x94NCH3xe2x80x94CH2xe2x80x94NCH3xe2x80x94 or xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94.
In another embodiment of the present invention, the catalytically active components used comprise compounds of the formula I b 
where
Z1 to Z4 independently of one another are
hydrogen;
halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred;
C1-C18 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C1-C6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, with particular preference C1-C4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
C1-C12 alkyl substituted one or more times by donor atoms, e.g., noncyclic or cyclic ethers, alcohols, ketals, thioethers or amines; for example, methoxymethyl, ethoxymethyl, ethoxyethyl, xcex2-hydroxyethyl, xcfx89-ethoxypropyl, (2-ethylhexyloxy)propylidene, methoxyethoxypropylidene or xcfx89-dimethylaminopropyl;
mono- or polyhalogenated C1-C12 alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, with particular preference fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
C2-C12 alkenyl, preferably C2 to xcfx89-C8 alkenyl such as vinyl, allyl, but-3-en-1-yl, xcfx89-pentenyl, xcfx89-hexenyl, xcfx89-heptenyl, and xcfx89-octenyl;
C3-C12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
C7 to C20 aralkyl, preferably C7 to C12 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, with particular preference benzyl;
C6-C14 aryl such asphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, with particular preference phenyl;
silyl SiR10R11R12, R10 to R12 independently of one another being selected from hydrogen, C1-C12 alkyl, C7-C15 aralkyl and C6-C14 aryl; preference is given to the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylylsilyl group; particular preference is given to the trimethylsilyl group and the tert-butyldimethylsilyl group;
siloxy OSiR10R11R12, R10 to R12 independently of one another being selected from hydrogen, C1-C12 alkyl, C7-C15 aralkyl and C6-C14 aryl; preference is given to the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxy and the tri-para-xylylsilyloxy group; particular preference is given to the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group;
C1-C12 alkoxy, preferably C1-C6 alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy and isohexoxy, with particular preference methoxy, ethoxy, n-propoxy and n-butoxy;
C6-C14 aryl, substituted in turn by one or more C1-C12 alkyl, C1-C12 alkenyl, C3-C12 cycloalkyl, C6-C14 aryl, silyl SiR10R11R12, siloxy OSiR10R11R12 or C1-C12 alkoxy groups, these groups being as specified above;
A2 is selected from oxygen, sulfur, Nxe2x80x94R13 or Pxe2x80x94R13, preferably Nxe2x80x94R13 or Pxe2x80x94R13, where R13 is as specified above.
In one particular embodiment of the present invention, two adjacent radicals may together and including the parent aromatic form a 5- to 10-membered ring. So in formula I b, for example, R3 and R4 or Z1 and Z2 may together be the following:
xe2x80x94(CH2)3xe2x80x94(trimethylene), xe2x80x94(CH2)4xe2x80x94(tetramethylene), xe2x80x94(CH2)5xe2x80x94(pentamethylene), xe2x80x94(CH2)6xe2x80x94(hexamethylene), xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94CH2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Oxe2x80x94CH2xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CH(CH3)xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CHxe2x80x94(C6H5)xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94C(CH3)2xe2x80x94Oxe2x80x94, xe2x80x94NCH3xe2x80x94CH2xe2x80x94CH2xe2x80x94NCH3xe2x80x94, xe2x80x94NCH3xe2x80x94CH2xe2x80x94NCH3xe2x80x94 or xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94.
The other variables are as defined for formula I a.
In formula I c 
X3, X4 and X5 independently of one another are
halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being particularly preferred;
trifluoroacetate;
BF4xe2x88x92, PF6xe2x88x92or SbF6xe2x88x92,
C1-C18 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C1-C6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, with particular preference C1-C4 alkyl such as methyl, ethyl, n-propyl and n-butyl;
C3-C12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred,
C7 to C20 aralkyl, preferably C7 to C12 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, with particular preference benzyl,
C6-C14 aryl such asphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, with particular preference phenyl;
C1-C12 alkoxy, preferably C1-C6 alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy and isohexoxy, with particular preference methoxy, ethoxy, n-propoxy and n-butoxy; or
NR8R9, where R8 and R9 independently of one another are selected from hydrogen, C1-C12 alkyl, C2-C12 alkenyl and C6-C14 aryl, which may form a saturated or unsaturated 5- to 10-membered ring; preference is given to the dimethylamino, the diethylamino, the diisopropylamino, the methylphenylamino, and the diphenylamino group. Examples of amino groups with saturated rings are the N-piperidyl group and the N-pyrrolidinyl group; examples of amino groups with unsaturated rings are the N-pyrryl group, the N-indolyl group, and the N-carbazolyl group.
Preferably, X3 to X5 are the same; with very particular preference, X3 to X5 are chlorine.
Nu1 to Nu3 independently of one another are selected from N or P; preferably, Nu1 and Nu2 are each N, and with particular preference Nu1 to Nu3 are each N.
R14 to R16 are, independently of one another,
hydrogen;
halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred;
C1-C18 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C1-C6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, with particular preference C1-C4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
C1-C12 alkyl substituted one or more times by donor atoms, e.g., noncyclic or cyclic ethers, alcohols, ketals, thioethers or amines; for example, methoxymethyl, ethoxymethyl, ethoxyethyl, xcex2-hydroxyethyl, xcfx89-ethoxypropyl, (2-ethylhexyloxy)propylidene, methoxyethoxypropylidene or xcfx89-dimethylaminopropyl;
mono- or polyhalogenated C1-C12 alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, with particular preference fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
C2-C12 alkenyl, preferably C2 to xcfx89-C8 alkenyl such as vinyl, allyl, but-3-en-1-yl, xcfx89-pentenyl, xcfx89-hexenyl, xcfx89-heptenyl, and xcfx89-octenyl;
C3-C12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
C7 to C20 aralkyl, preferably C7 to C12 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, with particular preference benzyl;
C6-C14 aryl such asphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, with particular preference phenyl;
silyl SiR10R11R12, R10 to R12 independently of one another being selected from hydrogen, C1-C12 alkyl, C7-C15 aralkyl and C6-C14 aryl; preference is given to the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylylsilyl group; particular preference is given to the trimethylsilyl group and the tert-butyldimethylsilyl group;
siloxy OSiR10R11R12, R10 to R12 independently of one another being selected from hydrogen, C1-C12 alkyl, C7-C15 aralkyl and C6-C14 aryl; preference is given to the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxy and the tri-para-xylylsilyloxy group; particular preference is given to the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group;
C1-C12 alkoxy, preferably C1-C6 alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy and isohexoxy, with particular preference methoxy, ethoxy, n-propoxy and n-butoxy;
C6-C14 aryl, substituted in turn by one or more C1-C12 alkyl, C1-C12 alkenyl, C3-C12 cycloalkyl, C6-C14 aryl, silyl SiR10R11R12, siloxy OSiR10R11R12 or C1-C12 alkoxy groups, these groups being as specified above.
Preferably, R14 to R16 are the same.
R17 to R22 independently of one another are
hydrogen;
C1-C18 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C1-C6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, with particular preference C1-C4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
mono- or polyhalogenated C1-C12 alkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluorooethyl, perfluoropropyl and perfluorobutyl, with particular preference fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
C1-C12 alkyl substituted one or more times by donor atoms, e.g., noncyclic or cyclic ethers, alcohols, ketals, thioethers or amines; for example, methoxymethyl, ethoxymethyl, ethoxyethyl, xcex2-hydroxyethyl, xcfx89-ethoxypropyl, (2-ethylhexyloxy)propylidene, methoxyethoxypropylidene or xcfx89-dimethylaminopropyl;
C2-C12 alkenyl, preferably C2 to xcfx89-C8 alkenyl such as vinyl, allyl, but-3-en-1-yl, xcfx89-pentenyl, xcfx89-hexenyl, xcfx89-heptenyl, and xcfx89-octenyl;
C3-C12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
C7 to C20 aralkyl, preferably C7 to C12 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, with particular preference benzyl;
C6-C14 aryl such asphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, with particular preference phenyl;
silyl SiR10R11R12, R10 to R12 independently of one another being selected from hydrogen, C1-C12 alkyl, C7-C15 aralkyl and C6-C14 aryl; preference is given to the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylylsilyl group; particular preference is given to the trimethylsilyl group and the tert-butyldimethylsilyl group;
siloxy OSiR10R11R12, R10 to R12 independently of one another being selected from hydrogen, C1-C12 alkyl, C7-C15 aralkyl and C6-C14 aryl; preference is given to the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxy and the tri-para-xylylsilyloxy group; particular preference is given to the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group;
C1-C12 alkoxy, preferably C1-C6 alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy and isohexoxy, with particular preference methoxy, ethoxy, n-propoxy and n-butoxy;
C6-C14 aryl, substituted in turn by one or more C1-C12 alkyl, C1-C12 alkenyl, C3-C12 cycloalkyl, C6-C14 aryl, silyl SiR10R11R12, siloxy OSiR10R11R12 or C1-C12 alkoxy groups, these groups being as specified above.
Preferably, R17, R19 and R21 are each the same, and preferably R18, R20 and R22 are each hydrogen. With very particular preference, R17 to R22 are hydrogen. The triazacyclohexane ligands needed to synthesize these very particularly preferred compounds lend themselves particularly well to synthesis.
In one particular embodiment of the formula I c, two adjacent radicals may together form a saturated or unsaturated 4- to 9-membered ring; for example, two radicals together may be: C3-C9 alkylidene such as xe2x80x94(CH2)3xe2x80x94(trimethylene), xe2x80x94(CH2)4xe2x80x94(tetramethylene), xe2x80x94(CH2)5xe2x80x94(pentamethylene), xe2x80x94(CH2)6xe2x80x94(hexamethylene), xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94CH2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Oxe2x80x94CH2xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CH(CH3) xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CHxe2x80x94 (C6H5) xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94C(CH3)2xe2x80x94Oxe2x80x94, xe2x80x94N(CH3)xe2x80x94CH2xe2x80x94CH2xe2x80x94N(CH3)xe2x80x94, xe2x80x94N(CH3)xe2x80x94CH2xe2x80x94N(CH3)xe2x80x94 or xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94.
The other variables are as defined for formula I a.
The preparation of the transition metal complexes of the formula I a to c is known per se. Suitable syntheses for complexes of the formulae I a and b are found in DE-A 197 10 615, in A. Dxc3x6hring et al., Organometallics 2000, 19, 388 and also in J. C. Weber, Dissertation, MPI Mxc3xchlheim/Ruhr, 1999.
The preparation of triazacycloalkane ligands is known per se. Those for synthesis of the very particularly preferred compounds of the formula I c wherein R17 to R22 are each hydrogen and the radicals R14 to R16 are each the same lend themselves especially well to synthesis by mixing formaldehyde, in the form of formalin solution, for example, and the associated amine R14xe2x80x94NH2. Various synthesis pathways for these complex ligands are described, for example, in F. Weitl, et al. J. Am. Chem. Soc. 1979, 101 2728; M. Takahashi, S. Takamoto, Bull. Chem. Soc. Japan 1977, 50, 3413; T. Arishima et al., Nippon Kagaku Kaishi 1973, 1119; L. Christiansen et al. Inorg. Chem. 1986, 25, 2813; L. R. Gahan et al., Aust. J. Chem. 1982, 35, 1119; B. A. Sayer et al., Inorg. Chim. Acta, 1983, 77, L63; K Wieghardt et al., Z. Naturforsch., 1983, 38b, 81, and I. A. Fallis et al., J. Chem. Soc., Chem. Commun. 1998, 665.
The metal complexes, especially the chromium complexes, may be simply obtained by reacting the corresponding metal salts such as metal chlorides or metal carbonyls, for example, with the ligands, as, for example, in P. Chaudhuri, K. Wieghardt, Prog. Inorg. Chem. 1987, 35, 329, or G. P. Stahley et al., Acta Crystall. 1995, C51, 18.
So that the above complexes of the formulae I a to c are catalytically active, they are activated with a cation forming compound. Suitable cation forming compounds are selected aluminum or boron compounds containing electron withdrawing radicals (e.g., trispentafluorophenylborane, trispentafluorophenylaluminum, N,N-dimethylanilinium tetrakispentafluorophenylborate, tri-n-butylammonium tetrakispentafluorophenylborate, N,N-dimethylanilinium tetrakis(3,5-bisperfluoromethyl)phenylborate, tri-n-butylammonium tetrakis(3,5-bisperfluoromethyl)phenylborate, and tritylium tetrakispentafluorophenylborate). These activators for complexes of the formulae I a to c are described in DE-A 199 35 407, in PCT/EP 0002716 and in Angew. Chem., Int. Ed., 1994, Vol. 33, p. 1877. Preference is given to dimethylanilinium tetrakispentafluorophenylborate, tritylium tetrakispentafluorophenylborate and trispentafluorophenylborane.
If boron or aluminum compounds are used as activators for the complexes of formulae Ia to c, then they are generally used in a molar ratio of 1:10 to 10:1, based on M; preferably 1:2 to 5:1 and with particular preference 1:1.5 to 1.5:1.
Another suitable class of cation forming compounds comprises the aluminoxanes of the formulae II a to b.
The precise structure of the aluminoxanes is unknown. They comprise products obtained by careful partial hydrolysis of aluminum alkyls (see DE-A 30 07 725). These products exist not in pure form but rather as mixtures of open-chain and cyclic structures of type II a and b. It is presumed that these mixtures are in a dynamic equilibrium. 
In formula II a and b, the radicals R23, independently of one another, are
C1-C12 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C1-C6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl; methyl is particularly preferred;
C3-C12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preference is given to cyclopentyl, cyclohexyl and cycloheptyl;
C7 to C20 aralkyl, preferably C7 to C12 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, with particular preference benzyl; or
C6-C14 aryl such asphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, with particular preference phenyl; and
n is an integer from 0 to 40, preferably from 1 to 25, and with particular preference from 2 to 22.
In the literature there is also discussion of cagelike structures for aluminoxanes (Y. Koide, S. G. Bott, A. R. Barron Organometallics 1996, 15, 2213-26; A. R. Barron Macromol. Symp. 1995, 97, 15-25). Irrespective of what the structure of the aluminoxanes actually looks like, they are suitable activators for complexes of transition metals of the formulae I a to c.
Mixtures of various aluminoxanes are particularly preferred activators in those cases where polymerization is conducted in a paraffin solution, n-heptane or isododecane, for example. One particularly preferred mixture is that obtainable commercially from Witco GmbH as COMAO, having a formula of
[(CH3)0.9(iso-C4H9)0.1AlO]n.
In order to activate the complexes of formulae Ia to c with aluminoxanes, an excess of aluminoxane, based on M, is generally necessary. Useful molar ratios M:Al lie in the range from 1:10 to 1:10 to 1:10,000, preferably 1:50 to 1:1000 and with particular preference 1:100 to 1:500.
The selected complex of the formulae I a to c and the cation forming compound together form a catalyst system. The activity of said catalyst system may be increased further by adding one or more further aluminum alkyl compounds of the formula Al(R23)3.
By adding further aluminum alkyl of the formula Al(R23)3 or aluminoxanes it is possible to raise the activity of the catalyst system; aluminum alkyls of the formula Al(R23)3 or aluminoxanes may also act as molecular mass regulators. Another effective molecular mass regulator is hydrogen. The molecular mass may be regulated especially well by way of the reaction temperature and the residence time.
Modern industrial preparation processes for polyolefin waxes are solution processes, suspension processes, bulk polymerization processes in liquid or supercritical monomers, and gas phase processes, the latter including both stirred gas phases or gas phase fluidized bed processes.
For the complexes of the formulae I a to c to be suitable for use in suspension processes, bulk polymerization processes, or gas phase processes, it is advantageous to immobilize them on a solid support. Otherwise, there may be morphology problems of the polymer (lumps, wall deposits, blockages in lines or heat exchangers) forcing plant shutdown. Supported complexes of the formulae I a to c are known from DE-A 199 35 407.
Very suitable monomers are ethylene and C3- to C10-alk-1-enes, i.e., propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. The monomers used are preferably ethylene and/or propylene.
The monomers may be homopolymerized or copolymerized with one another in any ratio. Preferred polyolefins on which the oxidized waxes are based are ethylene homopolymers having a density in the range from 0.90 to 0.98 g/cm3, preferably in the range from 0.94 to 0.97 g/cm3 and an Mw, determined by the method of GPC as described above, in the range from 1000 to 40,000 g/mol, preferably in the range from 2000 to 20,000 g/mol.
Further suitable polyolefin starting materials are ethylene/C3- to C10-alk-1-ene copolymers in which the overall amount of structural units deriving from the alk-1-ene or alk-1-enes is in the range from 0.1 to 15 mol %, preferably in the range from 1 to 10 mol %, based on the copolymer. Preferred ethylene/alk-1-ene copolymers are ethylene-propylene copolymers having a content of propylene derived structural units in the copolymer in the range from 0.1 to 10 mol %, preferably in the range from 1 to 5 mol %, based on the copolymer. The copolymers generally have an Mw, determined by the method of GPC as described above, in the range from 1000 to 40,000 g/mol, preferably in the range from 2000 to 20,000 g/mol.
Further preferred polyolefins on which the oxidized waxes are based are isotactic propylene homopolymers having an isotactic pentad content mmmm, determined by the method of 13C-NMR spectroscopy, in the range from 90 to 98% and an Mw, determined by the method of GPC as described above, in the range from 1000 to 40,000 g/mol, preferably in the range from 2000 to 20,000 g/mol.
Moreover, copolymers of propylene with ethylene and/or C4- to C10-alk-1-enes are also suitable as base polyolefins. In the propylene copolymers, the total amount of structural units deriving from the ethylene and/or the C4xe2x80x94 to C10-alk-1-enes is in the range from 0.1 to 15 mol %, preferably in the range from 1 to 10 mol %, based on the copolymer. Preferred propylene copolymers are propylene-ethylene copolymers having an ethylene derived structural unit content in the range from 0.1 to 10 mol %, preferably in the range from 1 to 5 mol %, based on the copolymer. The propylene copolymers generally have an Mw, determined with the method of GPC as described above, in the range from 1000 to 40,000 g/mol, preferably in the range from 1000 to 20,000 g/mol.
The monomers are homopolymerized or copolymerized in the presence of complexes of the formulae I a to c.
Suitable reactors for preparing the polymers or copolymers include continuous stirred tank reactors, the use of a row of serially connected stirred tanks being possible if desired. The polymerization reactions may be conducted in the gas phase, in suspension, in liquid and in supercritical monomers, or in inert solvents.
The oxidation of the polyolefins on which the oxidized waxes are based may be conducted with pure oxygen or with gases comprising oxygen. Preferably, air is used to oxidize the polyolefins. To support the oxidation, organic peroxides, such as di-tert-butyl peroxide, may be added; the addition of heavy metal salts such as manganese acetate is also conceivable. Moreover, it is possible to add organic or inorganic acids in order to accelerate the oxidation reaction. Suitable inorganic acids are hydrochloric acid or nitric acid. As organic acids, mention may be made of mono-, di- or tricarboxylic acids. Suitable monocarboxylic acids have 1 to 3 carbon atoms, formic and acetic acid being preferred. Higher monocarboxylic acids are less preferred owing to their unpleasant odor. Suitable dicarboxylic acids have 2 to 6 carbon atoms. Preferred dicarboxylic acids that may be mentioned by way of example include oxalic acid, malonic acid, maleic acid, tartaric acid, malic acid, and adipic acid. Particularly preferred dicarboxylic acids are tartaric acid, malic acid and adipic acid; a particularly preferred tricarboxylic acid is citric acid. Since acetic acid and adipic acid are frequently formed in the course of the oxidation, the addition of further acid is, however, not absolutely necessary.
Suitable oxidation processes for polyolefin waxes are known in principle, for example, from DE-A 20 35 706.
In one preferred process, the metallocene polyolefin of the invention, preferably an ethylene homopolymer, is reacted with oxygen-comprising gases, preferably air, in a tube reactor or stirred autoclave at a temperature in the range from 140 to 350xc2x0 C., preferably from 150 to 250xc2x0 C., and at a pressure in the range from 100 to 20,000 kPa, preferably in the range from 500 to 4000 kPa. The amount of oxygen supplied is then generally in the range from 0.1 to 1000 l oxygen/hxc2x7kg wax, preferably in the range from 1 to 50 l oxygen/hxc2x7kg wax.
The oxidized polyolefin waxes obtainable, especially the oxidized waxes from ethylene homopolymer, have a ratio of acid number to saponification number in the range from 1:1 to 1:4, preferably in the range from 1:1 to 1:2.
The acid number is determined by means of titration in accordance with DIN 53402. The saponification number is determined by means of titration in accordance with DIN 53401. Suitable acid numbers are from 1 to 150 mg KOH/g, preferably 10 to 50 mg KOH/g, and with particular preference from 15 to 30 mg KOH/g. The melting point of the oxidized waxes of the invention, determined by the method of Differential Scanning Calorimetry (DSC), in accordance with DIN 51007, is usually within a range from 90 to 125xc2x0 C., preferably within a range from 110 to 125xc2x0 C.
The hardness of the oxidized waxes of the invention is determined by the method of ball pressure hardness in accordance with DIN 50133. It is situated usually within a range from 800 to 2000 N/mm2, preferably within a range from 1000 to 1500 N/mm2.
The viscosity of the oxidized waxes of the invention, measured by the Ubbelohde melt viscosity method at 140xc2x0 C. in accordance with DIN 51562, is usually in the range from 100 to 10,000 cSt, preferably in the range from 200 to 5000 cSt.
The waxes of the invention are highly suitable as coating compositions or as components in coating compositions. As a general rule, the coating composition features high hardness and high gloss.
For example, the oxidized waxes of the invention are especially suitable as components in floorcare or leathercare compositions, especially shoecare compositions.